JP2004276593A - Thermal recording material - Google Patents
Thermal recording material Download PDFInfo
- Publication number
- JP2004276593A JP2004276593A JP2003415118A JP2003415118A JP2004276593A JP 2004276593 A JP2004276593 A JP 2004276593A JP 2003415118 A JP2003415118 A JP 2003415118A JP 2003415118 A JP2003415118 A JP 2003415118A JP 2004276593 A JP2004276593 A JP 2004276593A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- recording material
- material according
- hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000463 material Substances 0.000 title claims abstract description 56
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 41
- -1 4,4'-diallyloxydiphenyl sulfone Chemical class 0.000 claims description 31
- 150000003457 sulfones Chemical class 0.000 claims description 19
- 238000004040 coloring Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical group C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
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- 230000035945 sensitivity Effects 0.000 abstract description 40
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- 230000007423 decrease Effects 0.000 description 5
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 150000002430 hydrocarbons Chemical group 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
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- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- 229920002678 cellulose Polymers 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- GIMDPFBLSKQRNP-UHFFFAOYSA-N 1,1-diphenylethanol Chemical compound C=1C=CC=CC=1C(O)(C)C1=CC=CC=C1 GIMDPFBLSKQRNP-UHFFFAOYSA-N 0.000 description 1
- OIYMUIUXMYAXIX-UHFFFAOYSA-N 1,1-diphenylpropan-1-ol Chemical compound C=1C=CC=CC=1C(O)(CC)C1=CC=CC=C1 OIYMUIUXMYAXIX-UHFFFAOYSA-N 0.000 description 1
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- QFGQQQYBIDSQDV-UHFFFAOYSA-N 1,3-bis(2-ethenoxyethoxy)benzene Chemical compound C=COCCOC1=CC=CC(OCCOC=C)=C1 QFGQQQYBIDSQDV-UHFFFAOYSA-N 0.000 description 1
- IBAQDKCEVPEJDU-UHFFFAOYSA-N 1,4-bis(phenylmethoxy)naphthalene Chemical compound C=1C=CC=CC=1COC(C1=CC=CC=C11)=CC=C1OCC1=CC=CC=C1 IBAQDKCEVPEJDU-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
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- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
本発明は感熱記録材料に関し、更に詳しくは、第一に耐薬品性、とくに耐可塑剤性において画像残存率に優れ、第二に高感度で地肌カブリが少なく、耐熱保存性に優れた感熱記録材料に関するものである。 The present invention relates to a heat-sensitive recording material, and more specifically, a heat-sensitive recording which is excellent in image resistance ratio, firstly in chemical resistance, especially in plasticizer resistance, high in sensitivity, less in background fog, and excellent in heat storage stability. It is about materials.
近年、情報の多様化やニーズの拡大に伴い、情報記録分野に於いて各種の記録材料が研究・開発され実用化されているが、なかでも感熱記録材料は、（１）加熱プロセスのみによる簡易な画像の記録が可能なこと、（２）必要な装置のメカニズムが簡単でコンパクト化が容易であり記録材料が取扱い易く安価であることなどの利点を有するため情報処理分野（卓上計算機、コンピュータ等のアウトプット）、医療計測用レコーダー分野、低、高速ファクシミリ分野、自動券売機分野（乗車券、入場券等）、感熱複写機分野、Ｐ０Ｓシステムのラベル分野等、多岐にわたり用いられている。 In recent years, with the diversification of information and the expanding needs, various types of recording materials have been researched, developed, and put into practical use in the information recording field. (2) The information processing field (desktop computer, computer, etc.) has advantages such as (2) the required mechanism of the device is simple, the compactness is easy, and the recording material is easy to handle and inexpensive. Output), medical measurement recorder field, low and high speed facsimile field, automatic ticket vending machine field (passenger ticket, admission ticket, etc.), thermal copying machine field, POS system label field and so on.
これら感熱記録材料の利用分野の中で、ＰＯＳシステムのラベル分野、特に弁当や惣菜といった画像の信頼性を重視する分野で、急速に使われるようになっており、包装等に使用される有機高分子材料に含有されている可塑剤や油脂類に対して高い保存安定性を要求する用途に使われ、またレシート・領収書などの数年間の保存安定性を要求する用途にも使われ、感熱記録材料への要求品質が年々高まっているのが現状である。そのために、染料・顕色剤・保存安定剤等の助剤の開発がなされているが、発色感度と画像の保存安定性とをバランス良く十分に満足できるものは未だ見出されていない。 Among the fields of application of these heat-sensitive recording materials, they are rapidly being used in the field of labels for POS systems, especially in fields where importance is placed on the reliability of images such as lunch boxes and prepared dishes, and the use of organic materials used in packaging and the like is increasing. Used for applications requiring high storage stability for plasticizers and fats and oils contained in molecular materials, and for applications requiring storage stability for several years such as receipts and receipts, At present, the required quality of recording materials is increasing year by year. For this purpose, auxiliaries such as dyes, color developers, and storage stabilizers have been developed. However, there has not yet been found any one which can sufficiently satisfy the color development sensitivity and the storage stability of an image.
このうち、特に可塑剤や油脂類に対して高い保存安定性を示す顕色剤として、分子量の高いものが開発されてきている。このような顕色材として、ジフェニルスルホン誘導体の高分子型顕色剤（特許文献１参照）、（ポリ）４−ヒドロキシ安息香酸誘導体（特許文献２参照）および高分子量のウレアウレタン化合物（特許文献３参照）が提案されている。これらの顕色剤は可塑剤や油脂類に対して高い保存安定性を示すが、発色感度が低いことが課題である。 Among them, those having a high molecular weight have been developed as a color developer exhibiting high storage stability particularly to plasticizers and fats and oils. Examples of such a color developing material include a polymer type developer of a diphenyl sulfone derivative (see Patent Document 1), a (poly) 4-hydroxybenzoic acid derivative (see Patent Document 2), and a high-molecular-weight urea urethane compound (see Patent Document 1). 3) has been proposed. These developers exhibit high storage stability against plasticizers and fats and oils, but have a problem of low color development sensitivity.
例えばジフェニルスルホン誘導体の高分子量の顕色剤は発色感度を補うため、低融点の顕色剤や増感剤を用いることが提案されている（特許文献４、５等参照）。しかしこれらは低融点の顕色剤や増感剤を用いて低エネルギー領域での画像発色濃度をあげることでみかけの発色感度を向上させているが、耐可塑剤性等の保存性試験に対して画像濃度の低下、すなわち画像残存率の低下が顕著に見られる。これは、見かけの画像発色濃度の部分は低融点の顕色剤や増感剤による画像発色濃度の部分であり、可塑剤や油脂類に対して容易に消色するためと考えられる。端的に言うならば、本来、高分子量の顕色剤が持っている耐薬品性が、発色感度を上げるための手段によって、最大の特徴である耐薬品性を失うことを意味する。つまり高分子量の顕色剤において、発色感度の向上と耐薬品性における画像残存率の向上との両立が課題である。 For example, it has been proposed to use a low-melting-point color developer or a sensitizer in order to supplement a color developing sensitivity with a high molecular weight color developer of a diphenyl sulfone derivative (see Patent Documents 4 and 5). However, they improve the apparent color sensitivity by increasing the image color density in the low energy region by using a low melting point developer or sensitizer. As a result, a decrease in image density, that is, a decrease in image remaining rate is remarkably observed. This is presumably because the apparent image color density portion is the image color density portion due to the low melting point developer or sensitizer, and easily decolorizes to plasticizers and oils. To put it simply, it means that the chemical resistance inherent in the high-molecular-weight developer loses the chemical resistance, which is the greatest feature, by means for increasing the color sensitivity. That is, in a high-molecular-weight developer, it is necessary to achieve both an improvement in color-forming sensitivity and an improvement in the residual ratio of an image in chemical resistance.
また上述のように、ロイコ染料や顕色剤と共融し、融点降下を起こす材料である低融点の顕色剤や増感剤を添加することが行われている。例えば、ジフェニルスルホン架橋型化合物を顕色剤として用い、これにアミノスルホニル基（−ＳＯ2ＮＨ2）を有する芳香族化合物を増感剤として用いることにより、記録感度を向上させることが提案されている（特許文献７参照）が、低融点化すると感度は向上するが、発色温度が低下するため、感度向上と共に地肌かぶりが低温で発生してくるという問題点が発生し、発色感度と耐熱性の両立が課題である。 Further, as described above, a low melting point developer and a sensitizer which are eutectic with the leuco dye and the developer and cause a decrease in the melting point are added. For example, it has been proposed to improve recording sensitivity by using a diphenylsulfone cross-linked compound as a color developer and using an aromatic compound having an aminosulfonyl group (—SO 2 NH 2 ) as a sensitizer. However, although the sensitivity is improved when the melting point is lowered, the color development temperature is lowered, so that the background fogging occurs at a low temperature along with the sensitivity improvement, and the color sensitivity and heat resistance are increased. Is a challenge.
上記問題点の改善（感度と地肌カブリの両立）のために、４−ヒドロキシ−４’−アリルオキシジフェニルスルホンとさまざまな高分子型顕色剤とを組み合わせることが提案されており（特許文献６参照）、耐熱性、感度、耐薬品性が両立されている。 It has been proposed to combine 4-hydroxy-4'-allyloxydiphenyl sulfone with various types of high-molecular color developers in order to improve the above-mentioned problem (to achieve both sensitivity and background fog) (Patent Document 6). See), heat resistance, sensitivity and chemical resistance are compatible.
また、他に感度を向上させる方法として、アンダーコート層として中空粒子を含む層を設け、その断熱効果によりサーマルヘッドからの熱エネルギーを有効に活用する方法や、ロイコ染料の分散操作において、乳化分散等の手法を使いサブミクロンに加工する方法等があるが、十分な感度が得られなかったり、地肌カブリが生じたりして、感度と保存安定性の両立はできていないのが現状であった。 Other methods for improving sensitivity include providing a layer containing hollow particles as an undercoat layer, effectively utilizing heat energy from a thermal head due to its heat insulating effect, and emulsifying dispersion in a leuco dye dispersion operation. There is a method of processing to submicron using such a method, etc., but at present it was not possible to obtain sufficient sensitivity or fog of the background, and it was not possible to achieve both sensitivity and storage stability .
本発明の第１の目的は、耐薬品性、とくに耐可塑剤性に優れ、画像残存率が限りなく１００％に近い感熱記録材料を提供することである。
また、本発明の第２の目的は、高感度で地肌カブリが少なく耐熱保存性に優れた感熱記録材料を提供することである。
A first object of the present invention is to provide a heat-sensitive recording material having excellent chemical resistance, particularly excellent plasticizer resistance, and having an image residual ratio as close to 100% as possible.
A second object of the present invention is to provide a heat-sensitive recording material having high sensitivity, low background fog, and excellent heat-resistant storage stability.
すなわち、従来法においては、高い発色濃度で、高感度で地肌カブリがなく、耐熱保存性に優れるという機能を付与すると、耐薬品性における画像保存率の低下（具体的に述べると、染料と顕色剤だけでは１００％に近い画像残存率を有していたものが増感剤等を含有することで６０％から８０％程度に低下すること）を招くという課題があったが、本発明は、画像残存率を高くするという課題と、高感度で地肌カブリがなく、耐熱保存性に優れたものとするという課題とを同時に達成することができる感熱記録材料を提供するものである。 That is, in the conventional method, if a function of providing high color density, high sensitivity, no background fog, and excellent heat-resistant storage stability is imparted, the image storage rate in chemical resistance is reduced (specifically, the dye and the dye are hardly exposed). However, the present invention has a problem in that the colorant alone has an image remaining rate close to 100%, but the content is reduced from about 60% to about 80% by containing a sensitizer or the like. Another object of the present invention is to provide a heat-sensitive recording material capable of simultaneously achieving the problem of increasing the image residual ratio and the problem of achieving high sensitivity, no background fog, and excellent heat-resistant storage stability.
本発明は、上記課題を解決するべく、検討を行った結果、感熱記録材料が次に記載するような構成を備えることにより、保存安定性を維持しながら感度向上を図ることができると共に、地肌カブリ性や耐熱性を向上させることができることを見出した。 The present invention has been studied in order to solve the above-mentioned problems, and as a result of conducting studies, it has been found that the thermosensitive recording material is provided with the configuration described below, whereby the sensitivity can be improved while maintaining the storage stability, and the background can be improved. It has been found that fog resistance and heat resistance can be improved.
すなわち、本発明は次の構成を有する。
（１）支持体上に、ロイコ染料および顕色剤を主成分とする感熱発色層を設けてなる感熱記録材料において、該感熱発色層中に４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと４，４’−ジアリルオキシジフェニルスルホンとを含有すると共に、下記一般式（Ｉ）で表されるジフェニルスルホン誘導体を顕色剤として含有することを特徴とする感熱記録材料。
That is, the present invention has the following configuration.
(1) In a heat-sensitive recording material having a heat-sensitive coloring layer containing a leuco dye and a color developer as main components on a support, 4-hydroxy-4'-allyloxydiphenyl sulfone and 4-hydroxy-4'-allyloxydiphenyl sulfone are contained in the heat-sensitive coloring layer. And 4'-diallyloxydiphenyl sulfone, and a diphenyl sulfone derivative represented by the following general formula (I) as a color developer.
［式中、ＸおよびＹは各々相異なってもよく直鎖または分枝を有してもよい炭素数１〜１２の飽和、あるいは不飽和エーテル結合を有してもよい炭化水素基であるか、または、 [In the formula, X and Y each represent a hydrocarbon group which may be different from each other and which may have a linear or branched C 1 to C 12 saturated or unsaturated ether bond, Or
もしくは Or
（Ｒはメチレン基またはエチレン基を表し、Ｔは水素原子、炭素数１〜４のアルキル基を表す）を表す。Ｒ1〜Ｒ6はそれぞれ独立にハロゲン原子、炭素数１〜６のアルキル基、アルケニル基を示す。また、ｍ、ｎ、ｐ、ｑ、ｒ、ｔは０〜４の整数を表し、２以上の時はＲ1〜Ｒ6はそれぞれ異なっていてもよい。ａは０〜１０の整数を表す。〕 (R represents a methylene group or an ethylene group, and T represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). R 1 to R 6 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group. Further, m, n, p, q, r, and t represent an integer of 0 to 4, and when they are 2 or more, R 1 to R 6 may be different from each other. a represents an integer of 0 to 10. ]
（２）４−ヒドロキシ−４’−アリルオキシジフェニルスルホン１００重量部に対し、４，４’−ジアリルオキシジフェニルスルホンを０．５〜１０重量部含有することを特徴とする上記（１）記載の感熱記録材料。
（３）４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと一般式（Ｉ）で表される化合物との重量比が、３：７〜７：３であることを特徴とする上記（１）または（２）記載の感熱記録材料。
（４）前記ロイコ染料が、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ペンチル）アミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−ｐ−トルイジノ）−６−メチル−７−アニリノフルオランのいずれかであることを特徴とする上記（１）〜（３）のいずれかに記載の感熱記録材料。
（５）前記ロイコ染料の平均粒子径が０．１μｍ〜０．３μｍであることを特徴とする上記（１）〜（４）のいずれかに記載の感熱記録材料。
（６）支持体と感熱記録層との間に、少なくとも中空粒子を含むアンダーコート層を設けたことを特徴とする上記（１）〜（５）のいずれかに記載の感熱記録材料。
（７）前記中空粒子が、熱可塑性樹脂を殻とし、中空率３０％以上で平均粒子径が０．４〜１０μｍであることを特徴とする上記（１）〜（６）のいずれかに記載の感熱記録材料。
(2) The above (1), wherein 4,4'-diallyloxydiphenylsulfone is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of 4-hydroxy-4'-allyloxydiphenylsulfone. Thermal recording material.
(3) The above-mentioned (1), wherein the weight ratio of 4-hydroxy-4′-allyloxydiphenyl sulfone to the compound represented by the general formula (I) is 3: 7 to 7: 3. (2) The heat-sensitive recording material according to the above.
(4) The leuco dye is 3-dibutylamino-6-methyl-7-anilinofluoran, 3-di (n-pentyl) amino-6-methyl-7-anilinofluoran, 3- (N- The heat-sensitive recording material according to any one of the above (1) to (3), which is any one of (ethyl-Np-toluidino) -6-methyl-7-anilinofluoran.
(5) The thermosensitive recording material as described in any one of (1) to (4) above, wherein the average particle diameter of the leuco dye is 0.1 μm to 0.3 μm.
(6) The thermosensitive recording material according to any one of (1) to (5), wherein an undercoat layer containing at least hollow particles is provided between the support and the thermosensitive recording layer.
(7) The hollow particles are made of a thermoplastic resin as a shell, have a hollow ratio of 30% or more, and have an average particle diameter of 0.4 to 10 µm. Heat-sensitive recording material.
（８）感熱記録層の上に印刷層を設けたことを特徴とする上記（１）〜（７）のいずれかに記載の感熱記録材料。
（９）上記（１）〜（８）のいずれかに記載の感熱記録材料の支持体の裏面に粘着層を設けたことを特徴とする感熱記録型ラベル。
（１０）上記（１）〜（８）のいずれかに記載の感熱記録材料を用いたことを特徴とする感熱記録磁気券紙。
（１１）上記（１）〜（８）のいずれかに記載の感熱記録材料からなる感熱記録型切符。
（１２）上記（１）〜（８）のいずれかに記載の感熱記録材料からなる感熱記録型ポイントカード。
(8) The heat-sensitive recording material according to any one of the above (1) to (7), wherein a printing layer is provided on the heat-sensitive recording layer.
(9) A thermosensitive recording type label comprising a thermosensitive recording material according to any one of the above (1) to (8), wherein an adhesive layer is provided on the back surface of the support.
(10) A heat-sensitive recording magnetic ticket using the heat-sensitive recording material according to any one of (1) to (8).
(11) A thermosensitive recording type ticket comprising the thermosensitive recording material according to any one of (1) to (8).
(12) A thermosensitive recording type point card comprising the thermosensitive recording material according to any one of (1) to (8).
本発明の感熱記録材料は耐薬品性、とくに耐可塑剤性において画像残存率に優れ、且つ高感度で地肌カブリ少なく、耐熱保存性ともに優れたものであった。 The heat-sensitive recording material of the present invention was excellent in image resistance in chemical resistance, especially in plasticizer resistance, high in sensitivity, low in background fog, and excellent in heat storage stability.
本発明が前記作用効果を奏することの理由は明確ではないが、感度向上に関しては、４−ヒドロキシ−４’−アリルオキシジフェニルスルホンおよび一般式（Ｉ）で表されるジフェニルスルホン誘導体の相溶性が４，４’−ジアリルオキシジフェニルスルホンを添加することにより更に向上している為であると思われる。 Although it is not clear why the present invention exerts the above-mentioned effects, the compatibility between 4-hydroxy-4′-allyloxydiphenylsulfone and the diphenylsulfone derivative represented by the general formula (I) is not improved with respect to sensitivity. This is probably because the addition of 4,4'-diallyloxydiphenyl sulfone further improved.
また、地肌かぶり・耐熱かぶりに関しては、従来の感熱記録材料においては２種類以上の顕色剤を組合せて、一方をメインの顕色剤として用い、他方にはほとんど発色能のない化合物を用いるのが通常である。これは発色能のある顕色剤同士を組み合わせると地肌カブリが生じたり、耐熱性が極端に低下してしまう為であり、特許文献６において開示されている４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと本発明における一般式（Ｉ）で表されるジフェニルスルホン誘導体との組み合わせにおいても同様の現象が発生していると思われる。 Regarding background fogging and heat fogging, in a conventional thermosensitive recording material, two or more types of color developing agents are combined, one is used as a main color developing agent, and the other is a compound having almost no coloring ability. Is normal. This is because, when color developing agents are combined with each other, background fogging occurs or heat resistance is extremely reduced, and 4-hydroxy-4′-allyloxydiphenyl disclosed in Patent Document 6 is disclosed. It is considered that the same phenomenon occurs in the combination of sulfone and the diphenyl sulfone derivative represented by the general formula (I) in the present invention.
本発明においては、その作用は明確ではないが４，４’−ジアリルオキシジフェニルスルホンを添加することにより、ロイコ染料、４−ヒドロキシ−４’−アリルオキシジフェニルスルホンおよび一般式（Ｉ）の化合物からなる３成分系の場合の発色状態とは異なるものとなり、お互いが干渉しない状況を作り出している為と思われる。 In the present invention, the action is not clear, but by adding 4,4′-diallyloxydiphenylsulfone, the leuco dye, 4-hydroxy-4′-allyloxydiphenylsulfone and the compound of the general formula (I) can be obtained. This is different from the color development state in the case of the three-component system, and it is considered that a situation where they do not interfere with each other is created.
４，４’−ジアリルオキシジフェニルスルホンの添加量は、４−ヒドロキシ−４’−アリルオキシジフェニルスルホン１００重量部に対し、４，４’−ジアリルオキシジフェニルスルホンを０．５〜１０重量部含有することが好ましく、より好ましくは０．５〜５重量部で、特に好ましくは０．５〜１重量部である。
４−ヒドロキシ−４’−アリルオキシジフェニルスルホンが１０重量部以上の場合は、その相溶性が大きくなる為に、感度向上効果は大きくなるが、保存安定性（特に耐可塑剤性）の画像残存率が低下するので好ましくない。また、０．５重量部未満では相溶性の効果／地肌カブリ防止効果が小さくなり好ましくない。
The amount of 4,4'-diallyloxydiphenylsulfone added is 0.5 to 10 parts by weight of 4,4'-diallyloxydiphenylsulfone per 100 parts by weight of 4-hydroxy-4'-allyloxydiphenylsulfone. It is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 1 part by weight.
When the amount of 4-hydroxy-4'-allyloxydiphenyl sulfone is 10 parts by weight or more, the compatibility is increased, and the effect of improving the sensitivity is increased. However, the storage stability (particularly, plasticizer resistance) of the image remains. This is not preferable because the rate decreases. On the other hand, if the amount is less than 0.5 part by weight, the compatibility effect / background fog prevention effect becomes small, which is not preferable.
４，４’−ジアリルオキシジフェニルスルホンおよび４−ヒドロキシ−４’−アリルオキシジフェニルスルホンを上記比率に調整する方法としては、４，４’−ジアリルオキシジフェニルスルホンと４−ヒドロキシ−４’−アリルオキシジフェニルスルホンを上記比率に混合する方法および４−ヒドロキシ−４’−アリルオキシジフェニルスルホンの合成過程において、副生成物として合成される４，４’−ジアリルオキシジフェニルスルホンの比率を合成条件により調整する方法のどちらの方法を用いても構わない。 As a method of adjusting 4,4′-diallyloxydiphenyl sulfone and 4-hydroxy-4′-allyloxydiphenyl sulfone to the above-mentioned ratio, 4,4′-diallyloxydiphenyl sulfone and 4-hydroxy-4′-allyloxyl are used. In the method of mixing diphenylsulfone in the above ratio and in the process of synthesizing 4-hydroxy-4'-allyloxydiphenylsulfone, the ratio of 4,4'-diallyloxydiphenylsulfone synthesized as a by-product is adjusted according to the synthesis conditions. Either of the methods may be used.
４−ヒドロキシ−４’−アリルオキシジフェニルスルホンおよび一般式（Ｉ）
で示される顕色剤の添加量は、ロイコ染料１重量部に対して顕色剤全体で２〜７
重量部、好ましくは３〜５重量部が適当である。また、４−ヒドロキシ−４’−
アリルオキシジフェニルスルホンと一般式（Ｉ）で示される顕色剤との重量比は
３：７〜７：３、好ましくは４：６〜６：４でより好ましくは６：４〜５：５である。
４−ヒドロキシ−４’−アリルオキシジフェニルスルホンが顕色剤全体の３割に満たない場合は当然のことながら発色が不十分であり、また７割より過剰に使用した場合は、一般式（Ｉ）で示される顕色剤の保存安定性向上の効果が十分に得られない。
一般式（Ｉ）で表されるジフェニルスルホン誘導体におけるＸおよびＹは各々相異なってもよく直鎖または分枝を有してもよい炭素数１〜１２の飽和、あるいは不飽和エーテル結合を有してもよい炭化水素基であるか、または、次式で表される基である。
4-hydroxy-4'-allyloxydiphenyl sulfone and a compound of the formula (I)
Is 2 to 7 parts by weight as a whole with respect to 1 part by weight of the leuco dye.
A suitable amount is 3 parts by weight, preferably 3 to 5 parts by weight. Also, 4-hydroxy-4′-
The weight ratio of allyloxydiphenyl sulfone to the color developer represented by the general formula (I) is 3: 7 to 7: 3, preferably 4: 6 to 6: 4, more preferably 6: 4 to 5: 5. is there.
When 4-hydroxy-4'-allyloxydiphenyl sulfone accounts for less than 30% of the total color developer, the color development is naturally insufficient, and when it is used in excess of 70%, the compound represented by the general formula (I) ), The effect of improving the storage stability of the color developer cannot be sufficiently obtained.
X and Y in the diphenylsulfone derivative represented by the general formula (I) may be different from each other and may have a saturated or unsaturated ether bond having 1 to 12 carbon atoms which may be linear or branched. Or a group represented by the following formula:
ＸおよびＹの具体例としては、Ｘ及びＹは同じで、且つ飽和エーテル結合を有する炭素数１〜１２の炭化水素基が挙げられ、好ましくはＸ及びＹは同じで、且つ飽和エーテル結合を有する炭素数１〜６の炭化水素基挙げられ、Ｘ及びＹが同一でＣＨ２ＣＨ２ＯＣＨ２ＣＨ２であるものがもっとも好ましい。
また、Ｒは好ましくはＨ（水素原子）であり、Ｔは好ましくは水素原子、炭素数１〜４のアルキル基で、より好ましくは水素原子である。
Ｒ１〜Ｒ６はそれぞれ独立に好ましくは、ハロゲン原子、炭素数１〜４のアルキル基、アルケニル基で、より好ましくは炭素数１〜３のアルキル基である。
また、ｍ、ｎ、ｐ、ｑ、ｒ、ｔは好ましくは各々０〜４の整数で、より好ましくは０〜１である。
ａは好ましくは１〜１０の整数で、より好ましくは１〜７の整数である。
なお、一般式の化合物としては例えば日本曹達株式会社から商品名「Ｄ−９０」として市販されているものが使用できる。この「Ｄ−９０」は、一般式（Ｉ）において、Ｒ1〜Ｒ6がＨ（水素）、Ｘ及びＹが共にＣＨ2ＣＨ2ＯＣＨ2ＣＨ2 、ｍ〜ｔ＝４の化合物である。
As specific examples of X and Y, X and Y are the same and include a hydrocarbon group having 1 to 12 carbon atoms having a saturated ether bond. Preferably, X and Y are the same and have a saturated ether bond. Most preferred are hydrocarbon groups having 1 to 6 carbon atoms, wherein X and Y are the same and are CH 2 CH 2 OCH 2 CH 2 .
R is preferably H (hydrogen atom), and T is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.
R1 to R6 are each independently preferably a halogen atom, an alkyl group or alkenyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
Further, m, n, p, q, r, and t are each preferably an integer of 0 to 4, and more preferably 0 to 1.
a is preferably an integer of 1 to 10, more preferably an integer of 1 to 7.
As the compound of the general formula, for example, a compound commercially available from Nippon Soda Co. under the trade name "D-90" can be used. This “D-90” is a compound of the general formula (I) in which R 1 to R 6 are H (hydrogen), X and Y are both CH 2 CH 2 OCH 2 CH 2 , and m to t = 4.
本発明において、感熱発色層で用いられるロイコ染料は単独又は２種以上混合して適用されるが、このようなロイコ染料としては、この種の感熱記録材料に適用されているものが任意に適用され、例えば、トリフェニルメタン系、フルオラン系、フエノチアジン系、オーラミン系、スピロピラン系、インドリノフタリド系等の染料のロイコ化合物が好ましく用いられる。このようなロイコ染料の具体例としては、例えば、以下に示すようなものが挙げられる。 In the present invention, the leuco dye used in the thermosensitive coloring layer is applied alone or as a mixture of two or more, and as such a leuco dye, those applied to this kind of thermosensitive recording material can be arbitrarily applied. For example, leuco compounds of dyes such as triphenylmethane type, fluoran type, phenothiazine type, auramine type, spiropyran type and indolinophthalide type are preferably used. Specific examples of such a leuco dye include, for example, those shown below.
３，３−ビス（ｐ−ジメチルアミノフェニル）−フタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジメチル−アミノフタリド（別名クリスタルバイオレットラクトン）、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−ジエチルアミノフタリド、３，３−ビス（ｐ−ジメチルアミノフェニル）−６−クロルフタリド、３，３−ビス（ｐ−ジブチルアミノフェニル）フタリド、３−シクロヘキシルアミノ−６−クロルフルオラン、３−ジメチル−アミノ−５，７−ジメチル−フルオラン、３−Ｎ−メチル−Ｎ−イソブチル−６−メチル−７−アニリノフルオラン、３−Ｎ−エチル−Ｎ−イソアミル−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−７−クロロフルオラン、３−ジエチルアミノ−７−メチルフルオラン、３−ジエチルアミノ−７，８−ベンズフルオラン、３−ジエチルアミノ−６−メチル−７−クロルフルオラン、３−（Ｎ−ｐ−トリル−Ｎ−エチルアミノ−）−６−メチル−７−アニリノフルオラン、３−ピロリジノ−６−メチル−７−アニリノフルオラン、２−｛Ｎ−（３−トリフルオルメチル−フェニル）アミノ｝−１−６−ジエチルアミノ−フルオラン、２−｛３，６−ビス（ジエチルアミノ）−９−（ｏ−クロルアニリノ）キサンチル安息香酸ラクタム｝、３−ジエチルアミノ−６−メチル−７−（ｍ−トリクロロメチル−アニリノ）フルオラン、３−ジエチルアミノ−７−（ｏ−クロルアニリノ）フルオラン、３−ジブチルアミノ−７−（ｏ−クロルアニリノ）フルオラン、３−Ｎ−メチル−Ｎ−アミルアミノ−６−メチル−７−アニリノフルオラン、３−Ｎ−メチル−Ｎ−シクロヘキシルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−（２’，４’−ジメチルアニリノ）フルオラン、３−（Ｎ，Ｎ−ジエチルアミノ）−５−メチル−７−（Ｎ，Ｎ−ジベンジルアミノ−）フルオラン、ベンゾイルロイコメチレンブルー、６’−クロロ−８’−メトキシ−ベンゾインドリノースピロピラン、６’−ブロモ−３’−メトキシ−ベンゾインドリノースピロピラン、３−（２’−ヒドロキシ−４’−ジメチルアミノフェニル）−３−（２’−メトキシ−５’−クロルフェニル）フタリド、３−（２’−ヒドロキシ−４’−ジメチルアミノフェニル）−３−（２’−メトキシ−５’−ニトロフェニル）フタリド、３−（２’−ヒドロキシ−４’−ジエチルアミノフェニル）−３−（２’−メトキシ−５’−メチル−フェニル）フタリド、３−（２’−メトキシ−４’−ジメチル−アミノフェニル）−３−（２’−ヒドロキシ−４’−クロル−５’−メチル−フェニル）フタリド、３−モルホリノ−７−（Ｎ−プロピル−トリフルオロメチルアニリノ）フルオラン、３−ピロリジノ−７−トリフルオロメチル−アニリノフルオラン、３−ジエチルアミノ−５−クロロ−７−（Ｎ−ベンジルトリフルオロメチル−アニリノ）フルオラン、３−ピロリジノ−７−（ジ−ｐ−クロルフェニル）メチルアミノフルオラン、３−ジエチルアミノ−５−クロル−７−（α−フェニルエチルアミノ）フルオラン、３−（Ｎ−エチル−ｐ−トルイジノ）−７−（α−フェニルエチルアミノ）フルオラン、３−ジエチルアミノ−７−（ｏ−メトキシカルボニルフェニルアミノ）フルオラン、３−ジエチルアミノ−５−メチル−７−（α−フェニルエチルアミノ）フルオラン、３−ジエチルアミノ−７−ピペリジノフルオラン、２−クロロ−３−（Ｎ−メチルトルイジノ）−７−（ｐ−ｎ−ブチルアニリノ）フルオラン、３−（Ｎ−メチル−Ｎ−イソプロピルアミノ−）−６−メチル−７−アニリノフルオラン、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−エチル−７−（３−メチルアニリノ）フルオラン、３，６−ビス（ジメチルアミノ）フルオレンスピロ（９，３’）−６’−ジメチルアミノフタリド、３−（Ｎ−ベンジル−Ｎ−シクロヘキシルアミノ）−５，６−ベンゾ−７−α−ナフチルアミノ−４’−ブロモフルオラン、３−ジエチルアミノ−６−クロル−７−アニリノフルオラン、３−Ｎ−エチル−Ｎ−（２−エトキシプロピル）アミノ−６−メチル−７−アニリノフルオラン、３−Ｎ−エチル−Ｎ−テトラヒドロフルフリルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−メシチジノ−４’，５’−ベンゾフルオラン、３−（ｐ−ジメチルアミノフェニル）−３−｛１，１−ビス（ｐ−ジメチルアミノフェニル）エチレン−２−イル｝フタリド、３−（ｐ−ジメチルアミノフェニル）−３−｛１，１−ビス（ｐ−ジメチルアミノフェニル）エチレン−２−イル｝−６−ジメチルアミノフタリド、３−（ｐ−ジメチルアミノフェニル）−３−（１−ｐ−ジメチルアミノフェニル−１−フェニルエチレン−２−イル）フタリド、３−（ｐ−ジメチルアミノフェニル）−３−（１−ｐ−ジメチルアミノフェニル−１−ｐ−クロロフェニルエチレン−２−イル）−６−ジメチルアミノフタリド、３−（４’−ジメチルアミノ−２’−メトキシ）−３−（１”−ｐ−ジメチルアミノフェニル−１”−ｐ−クロロフェニルー１”，３”−ブタジエン−４”−イル）ベンゾフタリド、３−（４’−ジメチル−アミノ−２’−ベンジルオキシ）−３−（１”−ｐ−ジメチル−アミノ−フェニル−１”−フェニル−１”，３”−ブタジエンイ）イル｝ベンゾフタリド、３−ジメチルアミノ−６−ジメチルアミノフルオレン−９−スピロ−３’（６’−ジメチル−アミノ−）フタリド、３，３−ビス１２−（ｐ−ジメチルアミノフェニル）−２−（ｐ−メトキシフェニル）エテニル１−４，５，６，７−テトラクロロフタリド、３−ビス｛１，１−ビス（４−ピロリジノフェニル）エチレン−２−イル｝−５，６−ジクロロ−４，７−ジブロモフタリド、ビス（ｐ−ジメチルアミノスチリル）−１−ナフタレンスルホニルメタン、ビス（ｐ−ジメチルアミノスチリル）４−ｐ−トリルスルホニルメタン等が挙げられる。 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethyl-aminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethylamino) Phenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chlorofluoran , 3-dimethyl-amino-5,7-dimethyl-fluoran, 3-N-methyl-N-isobutyl-6-methyl-7-anilinofluoran, 3-N-ethyl-N-isoamyl-6-methyl- 7-anilinofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfuran Orchid, 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (Np-tolyl-N-ethylamino-)-6-methyl-7- Anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2- {N- (3-trifluoromethyl-phenyl) amino} -1-6-diethylamino-fluoran, 2- {3, Lactam 6-bis (diethylamino) -9- (o-chloroanilino) xanthylbenzoate, 3-diethylamino-6-methyl-7- (m-trichloromethyl-anilino) fluoran, 3-diethylamino-7- (o-chloroanilino ) Fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-amylamino-6-methyl -7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6 -Methyl-7- (2 ', 4'-dimethylanilino) fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino-) fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolinose pyropyran, 6'-bromo-3'-methoxy-benzoindolinose pyropyran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2 '-Methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-meth Toxi-5'-nitrophenyl) phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methyl-phenyl) phthalide, 3- (2'-methoxy- 4′-dimethyl-aminophenyl) -3- (2′-hydroxy-4′-chloro-5′-methyl-phenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethyl-anilinofluoran, 3-diethylamino-5-chloro-7- (N-benzyltrifluoromethyl-anilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) ) Methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran, 3- (N-E Ru-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino-5-methyl-7- (α-phenylethylamino ) Fluorane, 3-diethylamino-7-piperidinofluoran, 2-chloro-3- (N-methyltoluidino) -7- (pn-butylanilino) fluoran, 3- (N-methyl-N-isopropylamino- ) -6-Methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-ethyl-7- (3-methylanilino) fluoran, 3,6- Bis (dimethylamino) fluorenespiro (9,3 ′)-6′-dimethylaminophthalide, 3- (N-benzyl- -Cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4′-bromofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-ethyl-N- (2 -Ethoxypropyl) amino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7 -Mesitidino-4 ', 5'-benzofluoran, 3- (p-dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p -Dimethylaminophenyl) -3- {1,1-bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethyla Nophenyl) -3- (1-p-dimethylaminophenyl-1-phenylethylene-2-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (1-p-dimethylaminophenyl-1-p- Chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-2'-methoxy) -3- (1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3- (4'-dimethyl-amino-2'-benzyloxy) -3- (1" -p-dimethyl-amino-phenyl-1 "-phenyl- 1 ", 3" -butadiene) yl} benzophthalide, 3-dimethylamino-6-dimethylaminofluorene-9-spiro-3 '(6'-dimethyl-amino-) phthal 3,3-bis 12- (p-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl 1-4,5,6,7-tetrachlorophthalide, 3-bis @ 1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthalenesulfonylmethane, bis (p-dimethylaminostyryl) ) 4-p-tolylsulfonylmethane and the like.
なかでも、第一に耐薬品性、特に耐可塑剤性において画像残存率に優れ、第二に高感度で地肌カブリ少なく、耐熱保存性に優れた感熱記録材料を得る為には、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−ジ（ｎ−ペンチル）アミノ−６−メチル−７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ−ｐ−トルイジノ）−６−メチル−７−アニリノフルオランのいずれかを用いることが好ましい。 Among them, firstly, in order to obtain a heat-sensitive recording material having excellent image retention rate in terms of chemical resistance, particularly plasticizer resistance, and high sensitivity, low background fog, and excellent heat-resistant storage stability, 3-dibutyl is required. Amino-6-methyl-7-anilinofluoran, 3-di (n-pentyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-p-toluidino) -6 It is preferable to use any of methyl-7-anilinofluoran.
また本発明ではロイコ染料の平均粒子径が１．０μｍ以下の染料を用いることにより、高感度化は可能であるが、０．３μｍ以下にする事で更に高感度化を達成することが可能である。しかし、ロイコ染料の粒子径を小さくすることにより、地肌カブリが大きくなる傾向があり、染料粒子径が０．１μｍ以下になると地肌カブリが顕著に発生することから、地肌カブリと高感度とを両立させるには、０．１μｍ〜０．３μｍμｍにすることが好ましく、より好ましくは、０．１５μｍ〜０．２μｍである。 In the present invention, it is possible to increase the sensitivity by using a dye having an average particle diameter of 1.0 μm or less of the leuco dye, but it is possible to achieve higher sensitivity by adjusting the average particle diameter to 0.3 μm or less. is there. However, by reducing the particle size of the leuco dye, the background fog tends to increase, and when the dye particle size is 0.1 μm or less, the background fog is remarkably generated. In order to achieve this, the thickness is preferably set to 0.1 μm to 0.3 μm, and more preferably 0.15 μm to 0.2 μm.
地肌カブリの原因としては、通常ポリビニルアルコール等を分散剤として用いてロイコ染料を微粒子化分散した場合、粒径を小さくするほど分散液の着色濃度は高くなる。さらに顕色剤と混合した場合にはさらに着色が激しくなり感熱記録紙とした場合には地肌濃度が高くなる、このような原因としては、微粒子化する際の高い剪断応力によりポリビニルアルコールの未鹸化部分が変化し、酢酸ができる事で分散液のｐＨが低下し一部発色することや、染料粒子の一部が非結晶化し発色し易くなることが推定される。 As a cause of background fog, when a leuco dye is finely dispersed by using polyvinyl alcohol or the like as a dispersant, the coloring density of the dispersion becomes higher as the particle size becomes smaller. Furthermore, when mixed with a developer, the coloring becomes more intense, and the background density becomes higher when the recording paper is used as a heat-sensitive recording paper. This is because unsaponifiable polyvinyl alcohol is caused by high shearing stress when fine particles are formed. It is presumed that the pH of the dispersion is lowered due to the change of the part and the acetic acid is formed, and the color of the dispersion is partially developed, and that the dye particles are partially non-crystallized and the color is easily developed.
しかし、本発明の系では、ロイコ染料、４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと一般式（Ｉ）の３成分系の場合の発色状態とは異なり、お互いが干渉しない状況を作り出していると思われることから、微粒子化したロイコ染料を使用した場合でも地肌カブリの抑制にも効果を発揮していると考えられる。 However, in the system of the present invention, unlike the case of the leuco dye, 4-hydroxy-4'-allyloxydiphenyl sulfone and the three-component system of the general formula (I), a state in which they do not interfere with each other is created. Therefore, it is considered that even when the fine particle leuco dye is used, the effect of suppressing the background fog is exhibited.
また、分散剤としてノニオン系界面活性剤を主成分として用いて分散した場合にはｐＨの低下が少なく、染料の非結晶化を防止することができることから更に地肌カブリの抑制が可能である。 Further, when the dispersion is carried out by using a nonionic surfactant as a main component as a dispersant, the decrease in pH is small and the non-crystallization of the dye can be prevented, so that the background fog can be further suppressed.
本発明に使用される平均粒径０．３μｍ以下のロイコ染料は、界面活性剤をロイコ染料に対して重量部で５〜２０％含有させることが可能である。ロイコ染料の平均粒径を０．３μｍ以下にする分散方法としてはボールミル、アトライター、サンドミル、高圧ジェットミル等を用いる事ができるが、メディアを用いた分散方式が好ましく、メディアとして直径が０．５ｍｍ以下のジルコニアメディアを用いるか、または、メディア径が０．５ｍｍ〜１．０ｍｍのジルコニアメディアを用いて粗粉砕し、次いで０．５ｍｍ以下の径のジルコニアメディアを用いて分散することにより微粒子化が達成される。 The leuco dye having an average particle size of 0.3 μm or less used in the present invention can contain a surfactant in an amount of 5 to 20% by weight based on the leuco dye. A ball mill, an attritor, a sand mill, a high-pressure jet mill, or the like can be used as a dispersion method for controlling the average particle size of the leuco dye to 0.3 μm or less, but a dispersion method using a medium is preferable. Use zirconia media of 5 mm or less, or coarsely pulverize using zirconia media with a media diameter of 0.5 mm to 1.0 mm, and then disperse using zirconia media with a diameter of 0.5 mm or less to form fine particles. Is achieved.
本発明の感熱記録材料を構成する成分粒子の平均粒子径の測定方法は、例えばレーザー解析・散乱法によるか（マイクロトラックＨＲＡ９３２０−Ｘ１００型、堀場製作所製ＬＡ９２０型、レーゼンテックＦＢＲＭ装置）や遠心沈降方式、コールターカウンター、電子顕微鏡等、通常用いられている測定機により測定する事ができる。 The average particle diameter of the component particles constituting the heat-sensitive recording material of the present invention can be measured, for example, by a laser analysis / scattering method (Microtrac HRA9320-X100, LA920 manufactured by Horiba, Lazentec FBRM apparatus), or centrifugal sedimentation. It can be measured by a commonly used measuring instrument such as a method, a Coulter counter, and an electron microscope.
また本発明の感熱記録材料における顕色剤は、４−ヒドロキシ−４’−アリルオキシジフェニルスルホン、４，４’−ジアリルオキシジフェニルスルホンおよび前記一般式（Ｉ）で表されるジフェニルスルホン誘導体であるが、必要に応じて補助添加剤として、電子受容性であるが発色能力の比較的少ない種々のヒンダードフェノール化合物およびヒンダードアミン化合物を併用することができる。その具体例としては以下に示すようなものが挙げられる。 The color developer in the heat-sensitive recording material of the present invention is 4-hydroxy-4'-allyloxydiphenylsulfone, 4,4'-diallyloxydiphenylsulfone and the diphenylsulfone derivative represented by the general formula (I). However, if necessary, various hindered phenol compounds and hindered amine compounds which are electron-accepting but have relatively low coloring ability can be used in combination as auxiliary additives. Specific examples thereof include the following.
２，２’−メチレンビス（４−エチル−６−ターシャリーブチルフェノール）、４，４’−ブチリデンビス（６−ターシャリーブチル−２−メチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ターシャリブチルフェニル）ブタン、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル）ブタン、４，４’−チオビス（６−ターシャリーブチル−２−メチルフェノール）、テトラブロモビスフェノールＡ、テトラブロモビスフェノールＳ、４，４」チオビス（２−メチルフェノール）、４，４’−チオビス（２−クロロフェノール）、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート等。 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-2-methylphenol), 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-) Methylphenol), tetrabromobisphenol A, tetrabromobisphenol S, 4,4 "thiobis (2-methylphenol), 4,4'-thiobis (2-chlorophenol), tetrakis (1,2,2,6,6 -Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6 6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetra carboxylate.
本発明の感熱記録材料を製造するに際しては、ロイコ染料および顕色剤を支持体上に結合支持させるために慣用の種々の結合剤を適宜用いることができ、その具体例としては、例えば、以下のものが挙げられる。 In producing the thermosensitive recording material of the present invention, various conventional binders can be appropriately used for binding and supporting the leuco dye and the developer on the support. Specific examples thereof include, for example, One.
ポリビニルアルコール、澱粉およびその誘導体、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロース等のセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、アクリルアミド／アクリル酸エステル共重合体、アクリルアミド／アクリル酸エステル／メタクリル酸三元共重合体、スチレン／無水マレイン酸共重合体アルカリ塩、イソブチレン／無水マレイン酸共重合体アルカリ塩、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、カゼイン等の水溶性高分子の他、ポリ酢酸ビニル、ポリウレタン、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル／酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン／酢酸ビニル共重合体等のエマルジョンやスチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル系共重合体等のラテックス等。 Polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate copolymer, acrylamide / acrylate / methacrylic acid Water-soluble polymers such as terpolymers, styrene / maleic anhydride copolymer alkali salts, isobutylene / maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, casein, and polyvinyl acetate; Polyurethane, polyacrylic acid, polyacrylate, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, etc. Rujon and styrene / butadiene copolymer, styrene / butadiene / latex such as acrylic copolymer.
また本発明においては、その目的に応じて（例えば感度向上剤として）種々の熱可融性物質を使用することができるが、惣菜等の用途向けに耐熱性が要求される場合には、これらはできるだけ添加しないか、または融点が１００℃以上の化合物を選択して使用する必要がある。その具体例としては以下に示すものが挙げられるが、これらに限られるわけではない。 Further, in the present invention, various heat-fusible substances can be used depending on the purpose (for example, as a sensitivity improver). Must be added as little as possible or a compound having a melting point of 100 ° C. or higher must be selected and used. Specific examples include the following, but are not limited thereto.
ステアリン酸、べヘン酸等の脂肪酸類、ステアリン酸アミド、パルミチン酸アミド等の脂肪酸アミド類、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム、パルミチン酸亜鉛、ベヘン酸亜鉛等の脂肪酸金属塩類、ｐ−ベンジルビフェニル、ｍ−ターフェニル、ｐ−アセチルビフェニル、トリフェニルメタン、ｐ−ベンジルオキシ安息香酸ベンジル、β−ベンジルオキシナフタレン、β−ナフトエ酸フェニル、１−ヒドロキシー２−ナフト酸フェニル、１−ヒドロキシ−２−ナフトエ酸メチル、ジフェニルカーボネート、グレヤコールカーボネート、テレフタル酸ジベンジル、テレフタル酸ジメチル、１，４−ジメトキシナフタレン、１，４−ジエトキシナフタレン、１，４−ジベンジロキシナフタレン、１，２−ジフェノキシエタン、１，２−ビス（３−メチルフェノキシ）エタン、１，２−ビス（４−メチルフェノキシ）エタン、１，４−ジフェノキシ−２−ブテン、１，２−ビス（４−メトキシフェニルチオ）エタン、ジベンゾイルメタン、１，４−ジフェニルチオブタン、１，４−ジフェニルチオ−２−ブテン、１，３−ビス（２−ビニルオキシエトキシ）ベンゼン、１，４−ビス（２−ビニルオキシエトキシ）ベンゼン、ｐ−（２−ビニルオキシエトキシ）ビフェニル、ｐ−アリールオキシビフェニル、ｐ−プロパギルオキシビフェニル、ジベンゾイルオキシメタン、ジベンゾイルオキシプロパン、ジベンジルジスルフィド、１，１−ジフェニルエタノール、１，１−ジフェニルプロパノール、ｐ−ベンジルオキシベンジルアルコール、１，３−フェノキシ−２−プロパノール、Ｎ−オクタデシルカルバモイル−ｐ−メトキシカルボニルベンゼン、Ｎ−オクタデシルカルバモイルベンゼン、１，２−ビス（４−メトキシフェノキシ）プロパン、１，５−ビス（４−メトキシフェノキシ）−３−オキサペンタン、１，２−ビス（３，４−ジメチルフェニル）エタン、シュウ酸ジベンジル、シュウ酸ビス（４−メチルベンジル）、シュウ酸ビス（４−クロロベンジル）等。 Fatty acids such as stearic acid and behenic acid; fatty acid amides such as stearic acid amide and palmitic acid amide; fatty acid metal salts such as zinc stearate, aluminum stearate, calcium stearate, zinc palmitate and zinc behenate; Benzylbiphenyl, m-terphenyl, p-acetylbiphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, phenyl β-naphthoate, phenyl 1-hydroxy-2-naphthoate, 1-hydroxy- Methyl 2-naphthoate, diphenyl carbonate, gliacol carbonate, dibenzyl terephthalate, dimethyl terephthalate, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,2- Jife Nonoxyethane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-diphenoxy-2-butene, 1,2-bis (4-methoxyphenylthio) Ethane, dibenzoylmethane, 1,4-diphenylthiobutane, 1,4-diphenylthio-2-butene, 1,3-bis (2-vinyloxyethoxy) benzene, 1,4-bis (2-vinyloxyethoxy) ) Benzene, p- (2-vinyloxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, dibenzoyloxypropane, dibenzyldisulfide, 1,1-diphenylethanol, 1, 1-diphenylpropanol, p-benzyloxybenzyl alcohol, 1,3-phenyl Xy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoylbenzene, 1,2-bis (4-methoxyphenoxy) propane, 1,5-bis (4-methoxyphenoxy) -3- Oxapentane, 1,2-bis (3,4-dimethylphenyl) ethane, dibenzyl oxalate, bis (4-methylbenzyl) oxalate, bis (4-chlorobenzyl) oxalate and the like.
本発明における支持体として、上質紙、古紙パルプからなる支持体（古紙パルプを５０％以上使用）、合成紙、ラミネート紙等のいずれも用いることができる。
また支持体と感熱記録層との間のアンダーコート層や感熱記録層上にオーバーコート層を設けてもよい。アンダーコート層やオーバーコート層を形成する材料は、前記した感熱記録層に使用した結合剤、フィラー、架橋剤等が使用できる。
As the support in the present invention, any of a support made of high-quality paper and waste paper pulp (using at least 50% of waste paper pulp), synthetic paper, laminated paper, and the like can be used.
Further, an overcoat layer may be provided on the undercoat layer between the support and the thermosensitive recording layer or on the thermosensitive recording layer. As a material for forming the undercoat layer or the overcoat layer, the binder, filler, cross-linking agent, and the like used in the above-described heat-sensitive recording layer can be used.
アンダーコート層には中空樹脂粒子をフィラーとして用いるとその断熱性により感度を向上させる事ができるため特に好ましい。また、本発明において用いられる中空粒子は、熱可塑性樹脂を殻とし、内部に空気その他の気体を含有するもので、すでに発泡状態となっている微小中空粒子であり、平均粒子径は０．４〜１０μｍのものが用いられる。好ましくは１．０〜５．０μｍが好ましく、より好ましくは２．０μｍ〜４．０μｍである。 It is particularly preferable to use hollow resin particles as a filler for the undercoat layer because the heat insulating property can improve the sensitivity. The hollow particles used in the present invention are made of a thermoplastic resin as a shell, contain air or other gas inside, and are minute hollow particles already in a foamed state, and have an average particle diameter of 0.4. Those having a diameter of 10 to 10 μm are used. It is preferably from 1.0 to 5.0 μm, and more preferably from 2.0 to 4.0 μm.
この平均粒子径（粒子外径）が０．４μｍより小さいものは、任意の中空率にすることが難しい等の生産上の問題があり、逆に１０μｍより大きいものは、塗布乾燥後の表面の平滑性が低下するため、サーマルヘッドとの密着性が低下し、感度向上効果が低下する。従って、このような粒子分布は粒子径が前記範囲にあると同時に、バラツキの少ない分布ピークの均一なものが好ましい。 When the average particle diameter (particle outer diameter) is smaller than 0.4 μm, there is a problem in production such as difficulty in obtaining an arbitrary hollow ratio. Conversely, when the average particle diameter is larger than 10 μm, Since the smoothness is reduced, the adhesion to the thermal head is reduced, and the sensitivity improving effect is reduced. Therefore, it is preferable that such a particle distribution is such that the particle diameter is in the above-mentioned range and the distribution peak with a small variation is uniform.
更に、本発明で用いられる微小中空粒子は、中空率が３０％以上のものが好ましく、７０％以上のものが更に好ましく、９０％〜９８％の範囲が特に好ましい。なお、ここで言う中空率とは、中空粒子の外径と内径の比であり、下記式で表わされるものである。
中空率＝［（中空粒子の内径）／（中空粒子の外径）］×１００
なお、本発明で用いる微小中空粒子は、前記したように熱可塑性樹脂を殻とするものであるが、該樹脂としては、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸エステル、ポリアクリロニトリル、ポリブタジエンあるいはそれらの共重合体樹脂が挙げられる。
特に上記したような中空率を得る為には、塩化ビニリデンとアクリロニトリルを主体とする共重合体樹脂が好ましい。
通常、中空粒子は、感熱発色層と支持体の間に中間層として用いることにより、高い断熱性およびヘッドとの密着性を向上させ発色感度が向上する。
Further, the fine hollow particles used in the present invention preferably have a hollow ratio of 30% or more, more preferably 70% or more, and particularly preferably in the range of 90% to 98%. Here, the hollow ratio is a ratio of the outer diameter to the inner diameter of the hollow particles, and is represented by the following equation.
Hollow ratio = [(inner diameter of hollow particle) / (outer diameter of hollow particle)] × 100
The fine hollow particles used in the present invention have a shell made of a thermoplastic resin as described above. Examples of the resin include polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyacrylate. , Polyacrylonitrile, polybutadiene or their copolymer resins.
In particular, in order to obtain the above hollow ratio, a copolymer resin mainly composed of vinylidene chloride and acrylonitrile is preferable.
Usually, by using the hollow particles as an intermediate layer between the thermosensitive coloring layer and the support, the heat insulating property and the adhesion to the head are improved, and the coloring sensitivity is improved.
本発明の感熱記録材料の記録方法としては、使用目的によって熱ペン、サーマルヘッド、レーザー加熱等の記録方法があるが特に限定されない。
なお、支持体上に感熱発色層および保護層を形成するには従来公知の方法を用いればよく、支持体上に感熱発色層用塗布液および保護層用塗布液を順次塗布して乾燥させればよい。感熱発色層用塗布液および保護層用塗布液の塗布方法としては、ブレード塗布法、エアナイフ塗布法、グラビア塗布法、ロールコーティング塗布法、スプレー塗布法、ディップ塗布法、バー塗布法、エクストルージョン塗布法などの従来公知の塗布方法が利用できる。
As a recording method of the heat-sensitive recording material of the present invention, there are recording methods such as a hot pen, a thermal head, and laser heating depending on the purpose of use, but are not particularly limited.
A known method may be used to form the thermosensitive coloring layer and the protective layer on the support, and the thermosensitive coloring layer coating solution and the protective layer coating solution are sequentially coated and dried on the support. Just fine. The coating methods for the heat-sensitive coloring layer coating solution and the protective layer coating solution include blade coating, air knife coating, gravure coating, roll coating, spray coating, dip coating, bar coating, and extrusion coating. A conventionally known coating method such as a coating method can be used.
また本発明においては、必要に応じて、この種感熱記録材料に慣用される補助添加成分、例えば、填料、界面活性剤、滑剤、圧力発色防止剤等を併用することができる。この場合填料としては、例えば炭酸カルシウム、シリカ、酸化亜鉛、酸化チタン、水酸化アルミニウム、水酸化亜鉛、硫酸バリウム、クレーカオリン、タルク、表面処理されたカルシウムやシリカ等の無機系微粉末の他、尿素−ホルマリン樹脂、スチレン／メタクリル酸共重合体、ポリスチレン樹脂、塩化ビニリデン樹脂等の有機系の微粉末を挙げることができる、滑剤としては高級脂肪酸およびその金属塩、高級脂肪酸アミド、高級脂肪酸エステル、動物性、植物性、鉱物性又は石油系の各種ワックス類等があげられる。 Further, in the present invention, if necessary, auxiliary additives commonly used in this kind of heat-sensitive recording material, for example, fillers, surfactants, lubricants, pressure coloring inhibitors and the like can be used in combination. In this case, as the filler, for example, other than inorganic fine powders such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay kaolin, talc, surface-treated calcium and silica, Organic fine powders such as urea-formalin resin, styrene / methacrylic acid copolymer, polystyrene resin, vinylidene chloride resin and the like can be mentioned. As the lubricant, higher fatty acids and metal salts thereof, higher fatty acid amides, higher fatty acid esters, Examples include animal, vegetable, mineral or petroleum waxes.
なお、支持体上に感熱発色層および保護層を形成するには従来公知の方法を用いればよく、支持体上に感熱発色層用塗布液および保護層用塗布液を順次塗布して乾燥させればよい。オーバーコート層に有用な樹脂としては、例えば、ポリビニルアルコール、セルロース誘導体、澱粉およびその誘導体、カルボキシル基変性ポリビニルアルコール、ポリアクリル酸およびその誘導体、スチレン／アクリル酸共重合体およびその誘導体、ポリ（メタ）アクリルアミドおよびそれらの誘導体、スチレン／アクリル酸アクリル／アミド共重合体、アミノ基変性ポリビニルアルコール、エポキシ変性ポリビニルアルコール、ポリエチレンイミン、水性ポリエステル、水性ポリウレタン、イソブチレン／無水マレイン酸共重合体およびその誘導体等の水溶性樹脂や、ポリエステル、ポリウレタン、アクリル酸エステル系（共）重合体、スチレン／アクリル系共重合体、エポキシ樹脂、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリ塩化ビニルおよびこれらの誘導体が挙げられるが、中でもジアセトン変性ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール水溶性樹脂が好ましい。 A known method may be used to form the thermosensitive coloring layer and the protective layer on the support, and the thermosensitive coloring layer coating solution and the protective layer coating solution are sequentially coated and dried on the support. Just fine. Examples of useful resins for the overcoat layer include polyvinyl alcohol, cellulose derivatives, starch and derivatives thereof, carboxyl group-modified polyvinyl alcohol, polyacrylic acid and derivatives thereof, styrene / acrylic acid copolymer and derivatives thereof, and poly (meth) acrylate. ) Acrylamide and derivatives thereof, styrene / acrylic acid acryl / amide copolymer, amino group-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, polyethyleneimine, aqueous polyester, aqueous polyurethane, isobutylene / maleic anhydride copolymer and derivatives thereof, etc. Water-soluble resin, polyester, polyurethane, acrylate (co) polymer, styrene / acrylic copolymer, epoxy resin, polyvinyl acetate, polyvinylidene chloride, polyvinyl chloride Le and although their derivatives, among others diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol water-soluble resin.
また、オーバーコート層に加えられるフィラーとしては、例えば前述された感熱記録層に用いられるものと同様なものが適用可能であるが、水酸化アルミニウムやシリカなどが特に有用である。オーバーコート層に加えられるフィラーの量は、オーバーコート層全体の３０〜８０重量％、好ましくは４０〜７０重量％が適当である。オーバーコート層の付着量は２．０ｇ／ｍ2以下であり、これより多い付着量ではオーバーコート層の下側の感熱記録層への熱の移動に支障を来たすようになる。 As the filler to be added to the overcoat layer, for example, the same filler as that used in the above-described thermosensitive recording layer can be applied, but aluminum hydroxide and silica are particularly useful. The amount of the filler added to the overcoat layer is suitably 30 to 80% by weight, preferably 40 to 70% by weight of the entire overcoat layer. The adhesion amount of the overcoat layer is 2.0 g / m 2 or less, and if the adhesion amount is larger than this, the transfer of heat to the heat-sensitive recording layer below the overcoat layer is hindered.
次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの具体例に限定されるものではない。なお、以下に示す「部」および「％」は何れも重量基準である。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these specific examples. Note that “parts” and “%” shown below are based on weight.
［実施例１〜１４］および［比較例１〜６］
（１）感熱記録層を構成する各成分の調製
下記組成の〔Ａ液〕、〔Ｂ液〕、〔Ｃ液〕および〔Ｄ液〕の各液をサンドグラインダーを用いて、その平均粒径が、〔Ａ液〕については表１記載の粒子径となるように、また、〔Ｂ液〕〜〔Ｄ液〕については１．０μｍとなるように調製した。
[Examples 1 to 14] and [Comparative Examples 1 to 6]
(1) Preparation of each component constituting the heat-sensitive recording layer Each solution of [Solution A], [Solution B], [Solution C] and [Solution D] having the following composition was prepared using a sand grinder to obtain an average particle diameter. , [A solution] were adjusted to have the particle diameters shown in Table 1, and [Solution B] to [D solution] were adjusted to 1.0 μm.
〔Ａ液〕
表１記載のロイコ染料 ：２０部
ポリビニルアルコールの１０％水溶液 ：２０部
水 ：６０部
[A liquid]
Leuco dye described in Table 1: 20 parts 10% aqueous solution of polyvinyl alcohol: 20 parts Water: 60 parts
〔Ｂ液〕
４−ヒドロキシ−４’−アリルオキシジフェニルスルホン ：２０部
ポリビニルアルコールの１０％水溶液 ：２０部
非晶質シリカ ：１０部
水 ：５０部
[B liquid]
4-hydroxy-4'-allyloxydiphenyl sulfone: 20 parts 10% aqueous solution of polyvinyl alcohol: 20 parts Amorphous silica: 10 parts Water: 50 parts
〔Ｃ液〕
４，４’−ジアリルオキシジフェニルスルホン ：２０部
ポリビニルアルコールの１０％水溶液 ：２０部
水 ：６０部
[C liquid]
4,4'-diallyloxydiphenyl sulfone: 20 parts 10% aqueous solution of polyvinyl alcohol: 20 parts Water: 60 parts
〔Ｄ液〕
顕色剤（日本曹達社製Ｄ−９０） ：２０部
ポリビニルアルコールの１０％水溶液 ：２０部
水 ：６０部
[D liquid]
Developer (D-90, manufactured by Nippon Soda Co., Ltd.): 20 parts 10% aqueous solution of polyvinyl alcohol: 20 parts Water: 60 parts
（２）感熱記録層塗布液の調製
上記のようにして得た〔Ａ液〕〜〔Ｄ液〕を表１記載の割合で混合して実施例１〜１４、比較例１〜６で用いる感熱記録層塗布液を作製した。
(2) Preparation of coating solution for thermosensitive recording layer [Solution A] to [Solution D] obtained as described above were mixed at the ratios shown in Table 1 and used in Examples 1 to 14 and Comparative Examples 1 to 6. A recording layer coating solution was prepared.
（３）アンダーコート層形成液の調製
下記配合の［ａ液］および［ｂ液］をそれぞれ撹拌分散して、アンダーコート層形成液を調製した。
(3) Preparation of Undercoat Layer Forming Solution The following formulation [solution a] and [solution b] were each stirred and dispersed to prepare an undercoat layer forming solution.
［ａ液］
焼成カオリン ：２０部
スチレン／ブタジエン共重合ラテックス（固形分濃度47.5％） ：２０部
水 ：６０部
[Liquid a]
Calcined kaolin: 20 parts Styrene / butadiene copolymer latex (solid content: 47.5%): 20 parts Water: 60 parts
［ｂ液］
中空樹脂粒子 ：２５部
（中空率９０％、平均粒径３．５μｍ、固形分４０％）
スチレン／ブタジエン共重合ラテックス（固形分濃度47.5％） ：１５部
水 ：６０部
[Liquid b]
Hollow resin particles: 25 parts (hollow ratio: 90%, average particle size: 3.5 μm, solid content: 40%)
Styrene / butadiene copolymer latex (solid content 47.5%): 15 parts Water: 60 parts
（４）感熱記録紙の作製
坪量６０ｇ／ｍ2の紙上に上記で得た感熱発色塗工液を、染料付着量が０．５０ｇ／ｍ2になるように塗布乾燥し感熱発色層を設け、その後スーパーキャレンダーにて処理し、実施例１〜１２、比較例１〜４の感熱記録材料を得た。
また、坪量６０ｇ／ｍ2の紙上に上記で得たアンダーコート層形成液を乾燥塗布量が３．０ｇ／ｍ2になるように塗工し乾燥し、ついでその上に上記で得た感熱発色塗工液を、染料付着量が０．５０ｇ／ｍ2になるように塗布乾燥して感熱発色層を設け、その後スーパーキャレンダーにて処理し、実施例１３、１４、比較例５、６の感熱記録材料を得た。
(4) a thermal color-forming coating solution obtained above on paper fabrication basis weight of 60 g / m 2 of recording sheet, provided a coating dried thermosensitive coloring layer so that the amount of dye deposited is 0.50 g / m 2 Then, the resultant was treated with a super calender to obtain heat-sensitive recording materials of Examples 1 to 12 and Comparative Examples 1 to 4.
Further, the undercoat layer-forming liquid obtained above was coated on paper having a basis weight of 60 g / m 2 so that the dry coating amount was 3.0 g / m 2 , dried, and then the heat-sensitive material obtained above was applied thereon. The color-forming coating liquid was applied and dried so that the amount of dye applied was 0.50 g / m 2 to form a heat-sensitive color-forming layer, and then processed by a super calender. Examples 13 and 14, Comparative Examples 5 and 6 Was obtained.
（５）評価試験
以上のようにして作製した感熱記録材料について、下記試験を実施した。
（発色特性試験）
大倉電機（株）製感熱記録材料の印字シミュレーターにて、０．２７mj/dot、０３６mj/dot、０．４５mj/dotでエネルギーを印加して印字し、それぞれの発色濃度をマクベス濃度計ＲＤ−９１４にて測定した。
(5) Evaluation Test The following test was performed on the heat-sensitive recording material produced as described above.
(Coloring property test)
Applying energy at 0.27 mj / dot, 036 mj / dot, and 0.45 mj / dot with a printing simulator for thermal recording material manufactured by Okura Electric Co., Ltd. Was measured.
（耐熱性試験）
上記シミュレーターを用いてエネルギー０．４５mj/dotで印字した画像部および地肌部を８０℃の環境条件で２４時間放置した後の画像部および地肌部の濃度測定をした。
(Heat resistance test)
Using the above simulator, the density of the image portion and the background portion was measured after leaving the image portion and the background portion printed at an energy of 0.45 mj / dot at 80 ° C. for 24 hours.
（耐可塑剤性試験）
上記シミュレーターを用いてエネルギー０．４５mj/dotで印字した試験片に、塩ビラップを３枚重ね、さらに一般上質紙１０枚を重ね、約２００ｇ／ｃｍ2になるように重りをのせたものを、４０℃環境下で２４時間放置した後に、画像部および地肌部の濃度測定をした。以上の試験の結果を表２に示す。
(Plasticizer resistance test)
A test piece printed with an energy of 0.45 mj / dot using the simulator described above was laminated with three sheets of polyvinyl chloride wrap, and further laminated with 10 sheets of high quality paper, and a weight was placed so as to be about 200 g / cm 2 . After standing for 24 hours in a 40 ° C. environment, the density of the image area and the background area were measured. Table 2 shows the results of the above test.
表２に示された試験結果について説明する。
実施例１〜４を、比較例１（４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと一般式（Ｉ）で表されるジフェニルスルホン誘導体とを顕色剤として組み合わせた公知例）と対比すると、実施例１〜４では、比較例１のものに比して、４，４’−ジアリルオキシジフェニルスルホンを添加することによって感度が向上し、耐熱性試験後の地肌カブリおよび耐可塑剤性試験後の残存率が９０％から９１〜９２％に向上している。
比較例１のものは、耐可塑剤性試験後の画像残存率は高い水準を維持しているが、実施例１．２に対して感度が低く、また、耐熱性試験前および耐熱性試験後の地肌カブリが大きい。［耐熱性：比較例１（０．１９）、実施例１（０．１２）］
The test results shown in Table 2 will be described.
When Examples 1 to 4 are compared with Comparative Example 1 (a known example in which 4-hydroxy-4′-allyloxydiphenyl sulfone and a diphenyl sulfone derivative represented by the general formula (I) are combined as a color developer), In Examples 1 to 4, the sensitivity was improved by adding 4,4′-diallyloxydiphenyl sulfone as compared with that of Comparative Example 1, and the background fog after the heat resistance test and the after the plasticizer resistance test From 90% to 91 to 92%.
In Comparative Example 1, the image retention rate after the plasticizer resistance test was maintained at a high level, but the sensitivity was lower than that in Example 1.2, and before and after the heat resistance test. The fog of the ground is large. [Heat resistance: Comparative example 1 (0.19), Example 1 (0.12)]
実施例５〜１０は、４−ヒドロキシ−４’−アリルオキシジフェニルスルホンと一般式（Ｉ）で表されるジフェニルスルホン誘導体の添加量比および染料種を変化させた結果を示したものであり、いずれも良好な特性を示している。
比較例２〜３は従来例において染料種による違いを示したものであるが、実施例７、８のものに比べると感度が低く、耐熱性試験後の地肌カブリが大きくなっている。［耐熱性：比較例２（０．２０）］
Examples 5 to 10 show the results obtained by changing the addition amount ratio of 4-hydroxy-4′-allyloxydiphenyl sulfone and the diphenyl sulfone derivative represented by the general formula (I) and the dye type, All show good characteristics.
Comparative Examples 2 and 3 show the difference between the dye types in the conventional examples, but have lower sensitivity and larger background fog after the heat resistance test than those of Examples 7 and 8. [Heat resistance: Comparative example 2 (0.20)]
実施例１１〜１２は、実施例２のものに比べて染料の平均粒子径を小さくした場合を示したものであるが、実施例２のものよりも感度が向上している。
比較例４は、比較例１のものにおいて染料の平均粒子径を０．２μｍとしたものであり、感度向上効果はあるが、耐熱性試験前の地肌カブリ、耐熱性試験後の地肌カブリが共に大きい。［耐熱性：比較例４（０．２０）］
Examples 11 to 12 show the case where the average particle diameter of the dye was smaller than that of Example 2, but the sensitivity was improved as compared with that of Example 2.
In Comparative Example 4, the average particle diameter of the dye was 0.2 μm in Comparative Example 1, and although there was an effect of improving the sensitivity, the background fog before the heat resistance test and the background fog after the heat resistance test were both present. large. [Heat resistance: Comparative example 4 (0.20)]
実施例１３〜１４は、実施例２のものにアンダーコート層（プラスチック中空粒子を含む）を設けたものであるが、実施例２のものよりも感度が向上している。
比較例５、６は比較例１のものにおいてアンダーコート層を設けたものであり、感度向上効果はあるが、実施例のものに比べると耐熱性試験前の地肌カブリ、耐熱性試験後の地肌カブリが共に大きい。［耐熱性：比較例５、６（０．１９）］
In Examples 13 and 14, the undercoat layer (including the plastic hollow particles) was provided in Example 2, but the sensitivity was improved as compared with that in Example 2.
Comparative Examples 5 and 6 have the undercoat layer provided in Comparative Example 1 and have an effect of improving the sensitivity, but have a background fog before the heat resistance test and a background after the heat resistance test as compared with those of the examples. Both fog are large. [Heat resistance: Comparative Examples 5 and 6 (0.19)]
これらの比較例と本発明とを比較すると感度向上と耐熱性試験前の地肌カブリ・耐熱性試験後の地肌カブリの向上と耐可塑剤性の画像残存率の向上とが両立しており、その効果は明白である。 When comparing these comparative examples and the present invention, the improvement in sensitivity and the background fog before the heat resistance test and the improvement in the background fog after the heat resistance test and the improvement in the residual ratio of the plasticizer image are both compatible. The effect is obvious.
本発明の感熱記録材料は、耐薬品性、耐可塑剤性に優れ、高感度で地肌カブリが少なく、耐熱保存性に優れているので、情報処理分野（卓上計算機、コンピュータ等のアウトプット）、医療計測用レコーダー分野、低、高速ファクシミリ分野、自動券売機分野（乗車券、入場券等）、感熱複写機分野、Ｐ０Ｓシステムのラベル分野等における感熱記録材料とし適用することができる。 The heat-sensitive recording material of the present invention has excellent chemical resistance, plasticizer resistance, high sensitivity, low background fog, and excellent heat-resistant preservation. Therefore, the information processing field (output of a desktop computer, a computer, etc.) The present invention can be applied as a heat-sensitive recording material in the fields of medical measurement recorders, low-speed and high-speed facsimile machines, automatic ticket vending machines (passenger tickets, entrance tickets, etc.), heat-sensitive copying machines, POS system labels, and the like.
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| JP2003415118A JP4070712B2 (en) | 2003-02-28 | 2003-12-12 | Thermal recording material |
| ES04004566T ES2298635T3 (en) | 2003-02-28 | 2004-02-27 | THERMOSENSIBLE RECORDING MATERIAL. |
| EP04004566A EP1452334B1 (en) | 2003-02-28 | 2004-02-27 | Thermosensitive recording material |
| DE602004011128T DE602004011128T2 (en) | 2003-02-28 | 2004-02-27 | Heat-sensitive recording material |
| US10/788,262 US7078365B2 (en) | 2003-02-28 | 2004-03-01 | Thermosensitive recording material |
| CN2004100073653A CN1524710B (en) | 2003-02-28 | 2004-03-01 | Thermosensitive recording material |
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| JP2007275872A (en) * | 2006-03-16 | 2007-10-25 | Ricoh Co Ltd | Dispersion, heat-sensitive recording material and its manufacturing method |
| WO2014189044A1 (en) | 2013-05-22 | 2014-11-27 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
| WO2016125460A1 (en) * | 2015-02-04 | 2016-08-11 | 日本曹達株式会社 | Recording material and recording sheet |
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| JP4464232B2 (en) * | 2004-09-21 | 2010-05-19 | 株式会社リコー | Thermal recording material and thermal recording label |
| EP1702762B1 (en) * | 2005-03-14 | 2007-12-05 | Ricoh Company, Ltd. | Heat-sensitive recording material |
| US7425522B2 (en) * | 2006-01-18 | 2008-09-16 | Ricoh Company, Ltd. | Thermosensitive recording material |
| US20070225164A1 (en) * | 2006-03-16 | 2007-09-27 | Takeshi Kajikawa | Fluid dispersion, and thermosensitive recording material and method for preparing the same |
| US8003568B2 (en) * | 2006-09-15 | 2011-08-23 | Ricoh Company, Ltd. | Thermosensitive recording material |
| JP2008213390A (en) | 2007-03-07 | 2008-09-18 | Ricoh Co Ltd | Thermal recording material |
| JP5485749B2 (en) * | 2010-03-04 | 2014-05-07 | 三菱製紙株式会社 | Thermal recording material |
| CN103260888B (en) | 2010-12-07 | 2015-05-06 | 爱克发-格法特公司 | Method for colour laser marking of articles having polymer foil and the article comprising the polymer foil and colorless layer |
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2004
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- 2004-02-27 EP EP04004566A patent/EP1452334B1/en not_active Expired - Lifetime
- 2004-02-27 DE DE602004011128T patent/DE602004011128T2/en not_active Expired - Lifetime
- 2004-03-01 CN CN2004100073653A patent/CN1524710B/en not_active Expired - Lifetime
- 2004-03-01 US US10/788,262 patent/US7078365B2/en active Active
Cited By (10)
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|---|---|---|---|---|
| JP2007275872A (en) * | 2006-03-16 | 2007-10-25 | Ricoh Co Ltd | Dispersion, heat-sensitive recording material and its manufacturing method |
| WO2014189044A1 (en) | 2013-05-22 | 2014-11-27 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
| KR20160011658A (en) | 2013-05-22 | 2016-02-01 | 오지 홀딩스 가부시키가이샤 | Thermosensitive recording medium |
| US9789721B2 (en) | 2013-05-22 | 2017-10-17 | Oji Holdings Corporation | Thermosensitive recording medium |
| WO2016125460A1 (en) * | 2015-02-04 | 2016-08-11 | 日本曹達株式会社 | Recording material and recording sheet |
| KR20170104507A (en) * | 2015-02-04 | 2017-09-15 | 닛뽕소다 가부시키가이샤 | Recording material and recording sheet |
| JPWO2016125460A1 (en) * | 2015-02-04 | 2017-11-24 | 日本曹達株式会社 | Recording material and recording sheet |
| US20180022137A1 (en) * | 2015-02-04 | 2018-01-25 | Nippon Soda Co., Ltd. | Recording material and recording sheet |
| KR101940498B1 (en) | 2015-02-04 | 2019-01-21 | 닛뽕소다 가부시키가이샤 | Recording material and recording sheet |
| US10226957B2 (en) | 2015-02-04 | 2019-03-12 | Nippon Soda Co., Ltd. | Recording material and recording sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1452334A3 (en) | 2004-09-08 |
| ES2298635T3 (en) | 2008-05-16 |
| US7078365B2 (en) | 2006-07-18 |
| EP1452334A2 (en) | 2004-09-01 |
| JP4070712B2 (en) | 2008-04-02 |
| CN1524710A (en) | 2004-09-01 |
| CN1524710B (en) | 2010-06-16 |
| US20040171487A1 (en) | 2004-09-02 |
| DE602004011128T2 (en) | 2009-07-23 |
| EP1452334B1 (en) | 2008-01-09 |
| DE602004011128D1 (en) | 2008-02-21 |
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